CN103752280A - Composite modified walnut shell adsorbent as well as preparation method and application of composite modified walnut shell absorbent - Google Patents
Composite modified walnut shell adsorbent as well as preparation method and application of composite modified walnut shell absorbent Download PDFInfo
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Abstract
The invention discloses a composite modified walnut shell adsorbent as well as a preparation method and an application of the composite modified walnut shell adsorbent. The composite modified walnut shell adsorbent is prepared by taking a biologic material, namely the walnut shell, as a material, firstly, introducing amino groups by using epoxy chloropropane as an etherifying agent and diethylenetriamine as a cross-linking agent, and subsequently further performing composite modification reaction by using a silane coupling agent kh550. The adsorbent disclosed by the invention has excellent adsorption capacity, and is not only high in elimination rate for dyes in printing wastewater, but also is remarkable in treatment effect on heavy metal wastewater; raw materials used in the preparation method disclosed by the invention are wide in resource, and a prepared finished product is excellent in comprehensive property.
Description
Technical field
The invention belongs to modified adsorbent field of material preparation, particularly relate to composite modified walnut shell adsorbent for anionic dye in dyeing waste water and its preparation method and application.
Background technology
Along with the develop rapidly of China township enterprise and the further quickening of rural urbanization construction, the discharge of industrial wastewater and sanitary sewage day by day increases, particularly dyeing waste water, heavy metal polluted waste water are day by day serious on the impact of ecological environment and human health, it is carried out to respective handling and become in environmental improvement more and more distinct issues.Adsorption treatment dyeing waste water has proved a kind of simple method efficiently at present.Wherein charcoal absorption is because its method is simple, and operating the simple and easy and high many advantages that waits of removal efficiency has become most widely used wastewater processing technology at present, but consumption is large, cost is high and regeneration can produce secondary pollution etc. and limited its further development and application.
Many scholars are with agriculture and forestry by-product, as walnut shell, peanut shell, banana skin, pomelo peel and stalk etc., through a series of simple physical and chemical modified modifications, have made the adsorbent cheap, Selective adsorption is high, and have proved to have good effect.Find a kind of with low cost, easily obtain and the agriculture and forestry organic waste material of advantages of good adsorption effect is processed this class waste water as adsorbent and had theory and practical significance.
Chinese patent CN 200510040485.8 disclosed " a kind of utilize preparation method and the application of straw for cationic adsorption agent ", by the stalk citric acid-modified after pulverizing, backflow 12h, filter, distilled water is washed till neutrality, whole process complexity, property-modifying additive consumption is large, and cost is high; The people such as Yu Chunli are in Agriculture of Anhui science, 2009,37(20): in " the characterization of adsorption research of modified formaldehyde peanut shell to methylene blue " literary composition of delivering in 9618-9620 periodical, adsorption test by modified formaldehyde peanut shell to methylene blue, make to methylene blue have fine adsorptivity sorbing material, but the adsorbance to dyestuff is too little, and consumptive material is large; The people such as Huang Jiangsheng refer to modification tealeaves and Fe in " Study on adsorption properties of tealeaves matter iron to Reactive Brilliant Red K-2BP dyestuff and reactive brilliant yellow K-6G dyestuff " literary composition
3+reaction, makes sorbing material tealeaves matter iron, but all lower to the adsorbance of two kinds of dyestuffs, and best pH approaches 1, is difficult to promote the use of.Chinese patent application CN103223332A disclosed " a kind of modified silica-gel adsorbent containing amidoxime group and preparation method thereof " and Chinese patent application CN103223333A disclosed " a kind of silica gel absorber containing pair amidoxime groups and preparation method thereof of preparing ", the silica gel absorber scheme of preparation modification has all been proposed, though improve a lot compared with raw-material absorption property, but after modification, the maximal absorptive capacity of copper is also only had respectively to 20mg/g and 30mg/g, still have larger limitation.
In patent or paper, use walnut shell for dyestuff removal aspect, still to rarely have discovery as sorbent material, we find or using it directly as adsorbent absorbing dye, as SCI paper: Effective removal of Maxilon Red GRL from Aqueous solution by walnut shell:nonlinear Kinetic and Equilibrium Models, but discovery is also bad as the effect of adsorbent adsorption treatment of dye waste water with unmodified walnut shell, and adsorbance is only 10 ~ 50mg/g.Or have made active carbon, as SCI paper: Preparation of activated carbons from walnut shells via vacuum chemical activation and their application for methylene blue removal.But active carbon has cost high, the shortcomings such as difficult life.Moreover, SCI article by modification walnut shell sorbent treatment heavy metal wastewater thereby has: Removal of Cr (VI) from aqueous solutions by modified walnut shells, but modification walnut shell adsorbent is only also 30.99 mg/g to the saturated extent of adsorption of chromium.
For overcoming the deficiencies in the prior art, the applicant has proposed " a kind of preparation method of modification walnut shell cation adsorbent " in Chinese patent application 201310324695.4, the modified adsorbent that the method makes is the modification walnut shell cation adsorbent containing polyamino, to removing Reactive Brilliant Red K-2BP dyestuff in dyeing waste water, there is good effect, but also exist obviously not enough: the one, the amino amount of adsorbent surface grafting that this method of modifying makes is less, and it is still not enough to the adsorption capacity of dyestuff; The 2nd, the waste water type of processing with this modified adsorbent is very limited, as extremely low in the efficiency for adsorption treatment cation dyestuff and heavy metal wastewater thereby.
How to overcome the deficiencies in the prior art and become one of emphasis difficult problem urgently to be resolved hurrily in current modified adsorbent material technology field.
Summary of the invention
the technical problem solving:the present invention overcomes the deficiencies in the prior art and proposes composite modified walnut shell adsorbent and its preparation method and application.The present invention be large by contrast table area, mechanical strength is high, chemically stable good and the walnut shell of easy regeneration carries out modification, obtain modification walnut shell adsorbent, the experiment proved that it is not only high to the clearance of dyestuff in dyeing waste water, and the obvious processing effect to heavy metal wastewater thereby, the excellent combination property of prepared finished product product.
technical scheme:composite modified walnut shell adsorbent, its chemical structural formula is:
Composite modified walnut shell adsorbent described above particle diameter be 0.065 ~ 0.2mm.
The preparation method of composite modified walnut shell adsorbent described above, its concrete steps are as follows:
(1) by concentration, be that 0.5 ~ 1.5mol/L sodium hydroxide solution and epoxychloropropane add in cleaning the walnut shell after pulverizing and sieving, in every gram of walnut shell powder, add the sodium hydroxide solution of 5 ~ 20mL and the epoxychloropropane of 2 ~ 10mL; Then be placed in constant temperature combined reactor whip modified 40 ~ 90min at 40 ~ 65 ℃, then the walnut shell powder after modification spent to ionized water and be washed till after neutrality vacuum drying 3 ~ 5h at 65 ~ 100 ℃, make modification walnut shell powder one time;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the modification walnut shell powder that step (1) obtains, every gram of modification walnut shell powder adds the diethylenetriamine of 30 ~ 50mL deionized water, 0.1 ~ 2g sodium hydroxide powder and 5 ~ 20mL, then be placed in constant temperature combined reactor and stir 40 ~ 90min at 65 ~ 80 ℃, then the walnut shell powder after modification is spent to ionized water is washed till neutrality, vacuum drying 3 ~ 5h at 65 ~ 100 ℃, makes twice-modified walnut shell powder;
(3) the every gram of twice-modified walnut shell powder obtaining toward step (2) adds 1 ~ 10 mL silane coupler kh550 and 10 ~ 50mL N, dinethylformamide, at 60 ~ 85 ℃ at constant temperature combined reactor condensing reflux 0.5 ~ 2h, after reaction, filter use ethanol washing neutral and at 50 ~ 65 ℃ vacuum drying 3 ~ 8h, make composite modified walnut shell adsorbent finished product.
Preparation principle of the present invention is: composite modified walnut shell adsorbent of the present invention, be take biological material walnut shell as initiation material after pretreatment, first react with sodium hydroxide solution and epoxychloropropane etherifying agent, the modification walnut shell powder obtaining is reacted to introduce amino group with diethylenetriamine crosslinking agent, by the twice-modified walnut shell powder obtaining and the further grafting amino group of silane coupler kh550, make the composite modified walnut shell adsorbent finished product that outward appearance is brown color granular again.
Composite modified walnut shell adsorbent described above application in dyeing waste water and heavy metal-containing wastewater treatment.
Composite modified walnut shell adsorbent described above, when dyeing waste water and heavy metal-containing waste water, is admixed composite modified walnut shell adsorbent in dyeing waste water or heavy metal wastewater thereby, and the supernatant after precipitation is processes gained water.
Composite modified walnut shell adsorbent described above is when treatment of dyeing and printing, and the amount ratio of composite modified walnut shell adsorbent and dyeing waste water is (0.25 ~ 10) g: 1L; When processing heavy metal wastewater thereby, the amount ratio of composite modified walnut shell adsorbent and heavy metal wastewater thereby is (0.5 ~ 20) g: 1L.
Composite modified walnut shell adsorbent described above is when dyeing waste water and heavy metal-containing waste water, and design temperature is 20 ~ 30 ℃, and mixing time is 60 ~ 240min, and the sedimentation time is 20 ~ 30min.
beneficial effect:composite modified walnut shell adsorbent of the present invention and its preparation method and application compared with prior art, has significant advantage:
The one, the present invention uses specific area large, mechanical strength height and the good walnut shell of chemically stable, the composite modified walnut shell adsorbent making by method of the present invention, can be applied to dyeing waste water and heavy metal containing wastewater treatment field, its clearance to dyestuff in dyeing waste water is high, there is excellent adsorption capacity, especially a class is contained to hydroxy, sulfonic group, carboxyl, the dyestuff that can be combined with wool or silk fabric ionic bond and dye, through verification experimental verification, when addition is 0.5g/L, the azo dyes Reactive Brilliant Red K-2BP clearance that it is 200mg/L to concentration can reach 87.7 ~ 98.9%, adsorption capacity is about 15 times of unmodified walnut shell powder adsorbent, 4 ~ 5 times of commercially available coal mass active carbon adsorbent under equal experimental condition, 1.5 ~ 1.7 times of existing modification walnut shell cation adsorbent,
The 2nd, the treatment effect of ABSORBENTS ABSORPTION metallic wastewater of the present invention is more remarkable, through verification experimental verification, when addition is 1g/L, the heavy metal cadmium wastewater clearance that it is 50mg/L to concentration can reach 82.0 ~ 95.7%, adsorption capacity is approximately 10 times of unmodified walnut shell powder adsorbent, is 2.8 ~ 3.2 times of existing modification walnut shell cation adsorbent;
The 3rd, the mechanical strength of its finished product making of preparation method's needed raw material wide material sources of the present invention is high, chemically stable good, Heat stability is good and cost is low and easily regeneration, be widely used in applying in fields such as treatment of dyeing wastewater, heavy metal containing wastewater treatment, there is boundless application prospect.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of composite modified walnut shell adsorbent of the present invention.
Fig. 2 is the infrared spectrogram of the prepared composite modified walnut shell adsorbent of embodiment 3.
Fig. 3 is that the prepared composite modified walnut shell adsorbent of embodiment 3 amplifies the scanning electron microscope (SEM) photograph of 20000 times.
Fig. 4 amplifies the scanning electron microscope (SEM) photograph of 20000 times while being the prepared composite modified walnut shell adsorbent absorption azo dyes K-2BP of embodiment 3.
Fig. 5 amplifies the scanning electron microscope (SEM) photograph of 10000 times while being the prepared composite modified walnut shell adsorbent adsorbing heavy metal cadmium of embodiment 3.
The specific embodiment
Application test of the present invention has adopted has the representational azo dyes Reactive Brilliant Red K-2BP of dyestuff, and it is a kind of typical dye containing monoazo key.
embodiment 1
The present embodiment provides the preparation method of composite modified walnut shell adsorbent, and its manufacturing process comprises the following steps:
(1) by concentration, be that 0.5 mol/L sodium hydroxide solution and epoxychloropropane add in cleaning the walnut shell after pulverizing and sieving, in every gram of walnut shell powder, add the sodium hydroxide solution of 10 mL and the epoxychloropropane of 2 mL, then be placed in constant temperature combined reactor whip modified 60 min at 40 ℃, then the walnut shell powder after modification spent to ionized water and be washed till after neutrality vacuum drying 3h at 65 ℃;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the walnut shell powder that step (1) obtains, every gram of walnut shell powder adds the diethylenetriamine of 30 mL deionized waters, 1 g sodium hydroxide powder and 15 mL, then be placed on and in constant temperature combined reactor, at 65 ℃, stir 40 min, then the walnut shell powder after modification is spent to ionized water is washed till neutrality, vacuum drying 3h at 65 ℃;
(3) the every gram of dry powder obtaining toward step (2) adds 5 mL silane coupler kh550 and 10 mL N, dinethylformamide, at 60 ℃ at constant temperature combined reactor condensing reflux 1h, after reaction, filter use ethanol washing neutral and at 50 ℃ vacuum 5h, be composite modified walnut shell adsorbent finished product.
By this method of modifying, prepare the adsorbent obtaining and carry out adsorption test, setting initial activity bright red K-2BP concentration is 200 mg/L, and pH value of solution is 3, modified adsorbent dosage is 0.5g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate, measures K-2BP concentration.The composite modified walnut shell adsorbent of the method modification has reached 93.6% to the clearance of K-2BP, and adsorbance reaches 374.3 mg/g.
Setting containing cadmium heavy metal wastewater thereby initial concentration is 50 mg/L, and pH value of solution is 6, and modified adsorbent dosage is 1g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate.The clearance of the composite modified walnut shell ABSORBENTS ABSORPTION cadmium metal of the method modification has reached 91.3%, and adsorbance reaches 45.65 mg/g.
embodiment 2
The present embodiment provides the preparation method of composite modified walnut shell adsorbent, and its manufacturing process comprises the following steps:
(1) by concentration, be that 1.5 mol/L sodium hydroxide solutions and epoxychloropropane add in cleaning the walnut shell after pulverizing and sieving, in every gram of walnut shell powder, add the sodium hydroxide solution of 20 mL and the epoxychloropropane of 10 mL, then be placed in constant temperature combined reactor whip modified 40 min at 60 ℃, then the walnut shell powder after modification spent to ionized water and be washed till after neutrality vacuum drying 4h at 80 ℃;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the walnut shell powder that step (1) obtains, every gram of walnut shell powder adds the diethylenetriamine of 50 mL deionized waters, 0.1 g sodium hydroxide powder and 5 mL, then be placed on and in constant temperature combined reactor, at 75 ℃, stir 60 min, then the walnut shell powder after modification is spent to ionized water is washed till neutrality, vacuum drying 5h at 80 ℃;
(3) the every gram of dry powder obtaining toward step (2) adds 1 mL silane coupler kh550 and 30 mL N, dinethylformamide, at 70 ℃ at constant temperature combined reactor condensing reflux 0.5h, after reaction, filter use ethanol washing neutral and at 60 ℃ vacuum drying 8h, be composite modified walnut shell adsorbent finished product.
By this method of modifying, prepare the adsorbent obtaining and carry out adsorption test, setting initial activity bright red K-2BP concentration is 200 mg/L, and pH value of solution is 3, modified adsorbent dosage is 0.5g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate, measures K-2BP concentration.The composite modified walnut shell adsorbent of the method modification has reached 87.7 % to the clearance of K-2BP, and adsorbance reaches 350.8 mg/g.
Setting containing cadmium heavy metal wastewater thereby initial concentration is 50 mg/L, and pH value of solution is 6, and modified adsorbent dosage is 1g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate.The clearance of the composite modified walnut shell ABSORBENTS ABSORPTION cadmium metal of the method modification has reached 82.0%, and adsorbance reaches 41.00 mg/g.
embodiment 3
The present embodiment provides the preparation method of composite modified walnut shell adsorbent, and its manufacturing process comprises the following steps:
(1) by concentration, be that 1 mol/L sodium hydroxide solution and epoxychloropropane add in cleaning the walnut shell after pulverizing and sieving, in every gram of walnut shell powder, add the sodium hydroxide solution of 15 mL and the epoxychloropropane of 5 mL, then be placed in constant temperature combined reactor whip modified 90 min at 65 ℃, then the walnut shell powder after modification spent to ionized water and be washed till after neutrality vacuum drying 3h at 100 ℃;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the walnut shell powder that step (1) obtains, every gram of walnut shell powder adds the diethylenetriamine of 40 mL deionized waters, 2 g sodium hydroxide powder and 20 mL, then be placed on and in constant temperature combined reactor, at 80 ℃, stir 90 min, then the walnut shell powder after modification is spent to ionized water is washed till neutrality, vacuum drying 4h at 100 ℃;
(3) the every gram of dry powder obtaining toward step (2) adds 10 mL silane coupler kh550 and 50 mL N, dinethylformamide, at 85 ℃ at constant temperature combined reactor condensing reflux 2h, after reacting, filter and use ethanol washing neutrality and vacuum drying 8h at 65 ℃, be composite modified walnut shell adsorbent finished product, its infrared spectrogram is shown in Fig. 2.
By this method of modifying, prepare the adsorbent obtaining and carry out adsorption test, setting initial activity bright red K-2BP concentration is 200 mg/L, and pH value of solution is 3, modified adsorbent dosage is 0.5g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate, measures K-2BP concentration.The composite modified walnut shell adsorbent of the method modification has reached 98.9% to the clearance of K-2BP, and adsorbance reaches 395.5 mg/g.
Setting containing cadmium heavy metal wastewater thereby initial concentration is 50 mg/L, and pH value of solution is 6, and modified adsorbent dosage is 1g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate.The clearance of the composite modified walnut shell ABSORBENTS ABSORPTION cadmium metal of the method modification has reached 95.7%, and adsorbance reaches 47.85 mg/g.
embodiment 4
The present embodiment provides the preparation method of composite modified walnut shell adsorbent, and its manufacturing process comprises the following steps:
(1) by concentration, be that 0.8 mol/L sodium hydroxide solution and epoxychloropropane add in cleaning the walnut shell after pulverizing and sieving, in every gram of walnut shell powder, add the sodium hydroxide solution of 10 mL and the epoxychloropropane of 6 mL, then be placed in constant temperature combined reactor whip modified 60 min at 50 ℃, then the walnut shell powder after modification spent to ionized water and be washed till after neutrality vacuum drying 5h at 80 ℃;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the walnut shell powder that step (1) obtains, every gram of walnut shell powder adds the diethylenetriamine of 40 mL deionized waters, 1.5 g sodium hydroxide powder and 10 mL, then be placed on and in constant temperature combined reactor, at 65 ℃, stir 60 min, then the walnut shell powder after modification is spent to ionized water is washed till neutrality, vacuum drying 5h at 65 ℃;
(3) the every gram of dry powder obtaining toward step (2) adds 8 mL silane coupler kh550 and 20 mL N, dinethylformamide, at 80 ℃ at constant temperature combined reactor condensing reflux 1.5h, after reaction, filter use ethanol washing neutral and at 60 ℃ vacuum drying 8h, be composite modified walnut shell adsorbent finished product.
By this method of modifying, prepare the adsorbent obtaining and carry out adsorption test, setting initial activity bright red K-2BP concentration is 200 mg/L, and pH value of solution is 3, modified adsorbent dosage is 0.5g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate, measures K-2BP concentration.The composite modified walnut shell adsorbent of the method modification has reached 95.9% to the clearance of K-2BP, and adsorbance reaches 383.7 mg/g.
Setting containing cadmium heavy metal wastewater thereby initial concentration is 50 mg/L, and pH value of solution is 6, and modified adsorbent dosage is 1g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate.The clearance of the composite modified walnut shell ABSORBENTS ABSORPTION cadmium metal of the method modification has reached 93.1%, and adsorbance reaches 46.55 mg/g.
embodiment 5
The present embodiment provides the preparation method of composite modified walnut shell adsorbent, and its manufacturing process comprises the following steps:
(1) by concentration, be that 1.5 mol/L sodium hydroxide solutions and epoxychloropropane add in cleaning the walnut shell after pulverizing and sieving, in every gram of walnut shell powder, add the sodium hydroxide solution of 15 mL and the epoxychloropropane of 6 mL, then be placed in constant temperature combined reactor whip modified 60 min at 50 ℃, then the walnut shell powder after modification spent to ionized water and be washed till after neutrality vacuum drying 4h at 90 ℃;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the walnut shell powder that step (1) obtains, every gram of walnut shell powder adds the diethylenetriamine of 40 mL deionized waters, 2 g sodium hydroxide powder and 15 mL, then be placed on and in constant temperature combined reactor, at 70 ℃, stir 60 min, then the walnut shell powder after modification is spent to ionized water is washed till neutrality, vacuum drying 4h at 65 ℃;
(3) the every gram of dry powder obtaining toward step (2) adds 5 mL silane coupler kh550 and 30 mL N, dinethylformamide, at 70 ℃ at constant temperature combined reactor condensing reflux 1h, after reaction, filter use ethanol washing neutral and at 65 ℃ vacuum drying 6h, be composite modified walnut shell adsorbent finished product.
By this method of modifying, prepare the adsorbent obtaining and carry out adsorption test, setting initial activity bright red K-2BP concentration is 200 mg/L, and pH value of solution is 3, modified adsorbent dosage is 0.5g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate, measures K-2BP concentration.The composite modified walnut shell adsorbent of the method modification has reached 92.1% to the clearance of K-2BP, and adsorbance reaches 368.4 mg/g.
Setting containing cadmium heavy metal wastewater thereby initial concentration is 50 mg/L, and pH value of solution is 6, and modified adsorbent dosage is 1g/L, and oscillation rate is 160 rpm, adsorption time 2h, precipitate and separate.The clearance of the composite modified walnut shell ABSORBENTS ABSORPTION cadmium metal of the method modification has reached 89.6%, and adsorbance reaches 44.80 mg/g.
With composite modified walnut shell adsorbent provided by the invention at room temperature during treatment of dyeing and printing, composite modified walnut shell adsorbent addition is 1 ~ 2g/L, regulate pH to 2 ~ 5 of waste water from dyestuff, oscillation rate is 160 ~ 180r/min, when dye strength is 200 ~ 400mg/L, its clearance can reach 87.7 ~ 98.9%.
At room temperature process heavy metal wastewater thereby with composite modified walnut shell adsorbent provided by the invention, composite modified walnut shell adsorbent addition is 0.5 ~ 1g/L, regulate pH to 5.5 ~ 6.5 of cadmium wastewater, oscillation rate is 160 ~ 180r/min, when cadmium wastewater concentration is 30 ~ 50mg/L, its clearance can reach 82.0 ~ 95.7%.
Claims (6)
1. composite modified walnut shell adsorbent, is characterized in that chemical structural formula is:
2. composite modified walnut shell adsorbent according to claim 1, is characterized in that: described composite modified walnut shell adsorbent particle diameter be 0.065 ~ 0.2mm.
3. the preparation method of composite modified walnut shell adsorbent, is characterized in that concrete steps are as follows:
(1) by after clean walnut shell pulverizing and sieving, adding concentration is 0.5 ~ 1.5mol/L sodium hydroxide solution and epoxychloropropane, whip modified 40 ~ 90min at 40 ~ 65 ℃, be washed till after neutrality vacuum drying 3 ~ 5h at 65 ~ 100 ℃ by deionized water, make modification walnut shell powder one time, wherein: in every gram of walnut shell powder, add the sodium hydroxide solution of 5 ~ 20mL and the epoxychloropropane of 2 ~ 10mL;
(2) deionized water, sodium hydroxide powder and diethylenetriamine are added in the modification walnut shell powder that step (1) obtains, at 65 ~ 80 ℃, stir 40 ~ 90min, be washed till neutrality by deionized water, vacuum drying 3 ~ 5h at 65 ~ 100 ℃, make twice-modified walnut shell powder, wherein: every gram of modification walnut shell powder adds the diethylenetriamine of 30 ~ 50mL deionized water, 0.1 ~ 2g sodium hydroxide powder and 5 ~ 20mL;
(3) in the twice-modified walnut shell powder obtaining toward step (2), add silane coupler kh550 and N, dinethylformamide, condensing reflux 0.5 ~ 2h at 60 ~ 85 ℃, after reaction, filter, use ethanol washing to neutral and at 50 ~ 65 ℃ vacuum drying 3 ~ 8h, make composite modified walnut shell adsorbent finished product, wherein: in every gram of twice-modified walnut shell powder, add 1 ~ 10 mL silane coupler kh550 and 10 ~ 50mL DMF.
4. the application of composite modified walnut shell adsorbent in dyeing waste water and heavy metal-containing wastewater treatment.
5. the application of composite modified walnut shell adsorbent according to claim 4 in dyeing waste water and heavy metal-containing wastewater treatment, it is characterized in that: during treatment of dyeing and printing, the amount ratio of composite modified walnut shell adsorbent and dyeing waste water is (0.25 ~ 10) g: 1L, while processing heavy metal wastewater thereby, the amount ratio of composite modified walnut shell adsorbent and heavy metal wastewater thereby is (0.5 ~ 20) g: 1L.
6. the application of composite modified walnut shell adsorbent according to claim 4 in dyeing waste water and heavy metal-containing wastewater treatment, it is characterized in that: the design temperature for the treatment of of dyeing and printing and heavy metal wastewater thereby is 20 ~ 30 ℃, mixing time is 60 ~ 240min, and the sedimentation time is 20 ~ 30min.
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| CN105597700A (en) * | 2016-03-16 | 2016-05-25 | 华东交通大学 | Novel amino walnut shell adsorbent with efficient adsorption performance and preparation method thereof |
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